Azo dyes

ABSTRACT

Compounds of the formula ##STR1## in which K is the radical of a coupling component; 
     X is hydrogen, chloro, bromo, methyl or nitro; and 
     Y is hydrogen, chloro, bromo or methyl. 
     The compounds are eminently suitable as pigments for coloring printing inks, surface coatings and resins with exceptional fastness properties.

The invention relates to dyes of the general formula (I): ##STR2## in which K is the radical of a coupling component;

X is hydrogen, chloro, bromo, methyl or nitro; and

Y is hydrogen, chloro, bromo, or methyl.

Examples of coupling components are compounds of the phenol, naphthol, acetoacetarylide, pyrazolone, quinolone, pyridone, pyrimidone or isoquinolone series.

Preferred coupling components are represented by one of the members ##STR3## wherein Z is phenyl substituted by chloro, bromo, methyl, ethyl, methoxy, ethoxy, acetylamino, propionylamino, benzoylamino, chlorobenzoylamino or dichlorobenzoylamino; or ##STR4## A is ##STR5## PHENYL; PHENYL WHICH IS RING-SUBSTITUTED BY CHLORO, BROMO, METHYL, ETHYL, METHOXY, ETHOXY, CYANO, CARBAMOYL, N-phenylcarbamoyl, N-chlorophenylcarbamoyl, N-bromophenylcarbamoyl, N-methylphenylcarbamoyl, N-methoxyphenylcarbamoyl, N-ethoxyphenylcarbamoyl, C₁ to C₄ alkoxycarbonyl or sulfamoyl; naphthyl; anthraquinonyl; amino; C₁ to C₅ alkylamino; benzylamino; phenylamino; phenylamino which is ring-substituted by chloro, bromo, methyl, ethyl, methoxy, ethoxy or carbamoyl; naphthylamino; anthraquinonylamino; phenoxy; or phenoxy which is ring-substituted by chloro, bromo, methyl, ethyl, methoxy or ethoxy;

R¹ is hydrogen, chloro, bromo, C₁ to C₄ alkyl, C₁ to C₄ alkoxy, phenyl, methylsulfonyl, ethylsulfonyl, carbamoyl or sulfamoyl;

R² is hydrogen, chloro, bromo, methyl, ethyl, methoxy or ethoxy;

R³ is hydrogen, chloro, bromo, methyl or ethyl; and

R⁴ is hydrogen, chloro, bromo, methyl, ethyl, methoxy or ethoxy.

Examples of specific coupling components are: phenol, o-cresol, m-cresol, p-cresol, α-naphthol, β-naphthol, esters, amides and hydrazides of 2-naphthol-3-carboxylic acid, acetoacetanilide, acetoacet-o-anisidide, 1-phenyl-3-methylpyrazolone, 1-phenylpyrazolone-3-carboxylic esters or amides, 2,4-dihydroxyquinoline, N-methyl-4-hydroxyquinolone-2, 2,6-dihydroxy-3-cyano-4-methylpyridine, 2,6-dihydroxy-3-carbamoyl-4-methylpyridine, N-methyl-2-hydroxy-3-cyano-4-methylpyridone-6, N-y-methoxypropyl-2-hydroxy-3-cyano-4-methylpyridone-6, N-butyl-2-hydroxy-3-cyano-4-methylpyridone-6, 2-amino-4,6-dihydroxypyrimidine, 2,4-dihydroxy-6-aminopyrimidine, 2,4-diamino-6-hydroxypyrimidine, 1,3-dimethyl-4-hydroxypyrimidinedione-2,6 and 1,3-dihydroxyisoquinoline.

Dyes of the formula (I) may be prepared by reacting a diazo compound of an amine of the formula (II): ##STR6## with a coupling component of the formula (III):

    HK                                                         (III)

triazinones of the formula (IV): ##STR7## may also be reacted with coupling components of the formula (III) at elevated temperature and preferably in an inert organic solvent to form compounds of the formula (V): ##STR8## from which compounds of the formula (I) may be obtained by elimination of water by a conventional method, for example with thionyl chloride or phosgene.

To prepare dyes with 2-naphthol-3-carboxamide components it may be convenient to start from acid chlorides of the formula: ##STR9## and to convert these into the dye amides by reaction with the appropriate amines by a conventional method.

Dyes suitable as pigments include particularly the compounds of the formula (I) in which K is the radical of a coupling component of the β-naphthol, acetoacetarylide, pyrimidine, dihydroxyquinoline or dihydroxypyridine series. These dyes are distinguished by fairly great insolubility in conventional solvents and almost all of them exhibit as pigments high color strength, good fastness to overcoating, migration and overspraying and some of them very good lightfastness. The new dyes are suitable for example as disperse dyes for dyeing fibrous materials or as dyes for coloring high molecular weight organic material, for example cellulose ethers, cellulose esters, superpolyamides, superpolyurethanes, polyesters, acetylcellulose, nitrocellulose, natural resins or synthetic resins such as polymerization resins or condensation resins, for example aminoplasts and particularly urea-formaldehyde resins and melamineformaldehyde resins, alkyd resins, phenolic plastics, polycarbonates, polyolefins such as polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile, polyacrylic esters, rubber, casein, silicones and silicone resins. They are moreover suitable for the production of print pastes for various purposes, polymer dispersions and surface coatings, for example based on melamine resins, acrylate resins or other materials.

Pigments of the formula (I) are not always obtained in the optimum form for a specific purpose. They may however be converted into the most suitable form by known methods such as grinding with salt or heating in water or solvent.

A group of dyes particularly preferred industrially has the general formula (Ia): ##STR10## in which R¹ is hydrogen, chloro, bromo, C₁ to C₄ alkyl, C₁ to C₄ alkoxy, phenyl, methylsulfonyl, ethylsulfonyl, carbamoyl or sulfamoyl;

R² is hydrogen, chloro, bromo, methyl, ethyl, methoxy or ethoxy;

R³ is hydrogen, chloro, bromo, methyl or ethyl; and

R⁴ is hydrogen, chloro, bromo, methyl, ethyl, methoxy or ethoxy.

Another group of preferred dyes has the formula (Ib): ##STR11## in which A¹ is C₁ to C₄ alkyl; phenyl; phenyl substituted by chloro, bromo, methyl, ethyl, methoxy, ethoxy, cyano, carbamoyl, N-phenylcarbamoyl, N-chlorophenylcarbamoyl, N-bromophenylcarbamoyl, N-methylphenylcarbamoyl, N-methoxyphenylcarbamoyl, N-ethoxyphenylcarbamoyl, C₁ to C₄ alkoxycarbonyl or sulfamoyl; naphthyl; anthraquinonyl; amino; C₁ to C₅ alkylamino; benzylamino, phenylamino, phenylamino substituted by chloro, bromo, methyl, ethyl, methoxy, ethoxy or carbamoyl; naphthylamino; anthraquinonylamino, phenoxy; or phenoxy substituted by chloro, bromo, methyl, ethyl, methoxy or ethoxy; and R⁴ has the meanings given for formula (Ia).

The CONH-- and NHOC--groups are preferably in the para-position to one another.

R¹ is preferably hydrogen, chloro, bromo, methyl, ethyl, methoxy or ethoxy;

R² is preferably hydrogen, chloro, methyl, ethyl, methoxy or ethoxy;

R³ is preferably hydrogen, chloro or methyl; and

R⁴ is preferably hydrogen.

Pigments of the formula (Ia) are as a rule distinguished by a very brilliant hue, high tinctorial strength and excellent fastness properties, of which lightfastness, weathering fastness and migration fastness may be emphasized. The pigments may be used for all purposes where outstanding fastness properties are required.

In the following Examples, which will illustrate the invention, parts and percentages are by weight unless otherwise specified.

EXAMPLE 1

23.8 parts of 2-o-aminophenyl-4H-3,1-benzoxazin-4-one is introduced at 10° to 15° C into 100 parts of 96% sulfuric acid and diazotized at 0° to 5° C by adding 32 parts of nitrosylsulfuric acid (45%). The whole is stirred for another 2 hours at 5° C, poured onto a mixture of 500 parts of ice and 600 parts of water, then 33.8 parts of 2-naphthol-3-carboxylic acid-N-2'-methoxy-4'-nitrophenylamide is added and a pH of 6 is set up with dilute caustic soda solution. The whole is stirred for another five hours, suction filtered and washed thoroughly with hot water. The filtered material is then stirred in 250 parts of dimethylformamide for two hours at 120° C, suction filtered, washed with methanol and dried. 49.2 parts of a brilliant red powder is obtained which has the formula: ##STR12##

Dyes having the hues specified in the following Table are obtained analogously to Example 1 with the coupling components given in the Table:

    ______________________________________                                         Ex.                                                                            No.  Coupling component         Hue                                            ______________________________________                                               ##STR13##                 red                                            3                                                                                    ##STR14##                 red                                            4                                                                                    ##STR15##                 red                                            5                                                                                    ##STR16##                 red disp.                                      6                                                                                    ##STR17##                 red disp.                                      7                                                                                    ##STR18##                 red disp.                                      8                                                                                    ##STR19##                 yellowish red disp.                            9                                                                                    ##STR20##                 red disp.                                      10                                                                                   ##STR21##                 Bordeaux                                       11                                                                                   ##STR22##                 red                                            12                                                                                   ##STR23##                 yellow                                         13                                                                                   ##STR24##                 yellow                                         14                                                                                   ##STR25##                 yellow                                         15                                                                                   ##STR26##                 yellow                                         16                                                                                   ##STR27##                 yellow                                         17                                                                                   ##STR28##                 yellow                                         18                                                                                   ##STR29##                 yellow                                         19                                                                                   ##STR30##                 yellow                                         20                                                                                   ##STR31##                 yellow                                         21                                                                                   ##STR32##                 yellow                                         22                                                                                   ##STR33##                 yellow                                         23                                                                                   ##STR34##                 reddish yellow                                 24                                                                                   ##STR35##                 yellow                                         25                                                                                   ##STR36##                 yellow                                         26                                                                                   ##STR37##                 yellow disp.                                   27                                                                                   ##STR38##                 yellow disp.                                   28                                                                                   ##STR39##                 yellow                                         29                                                                                   ##STR40##                 reddish yellow                                 30                                                                                   ##STR41##                 yellow                                         31                                                                                   ##STR42##                 yellow                                         32                                                                                   ##STR43##                 yellow                                         33                                                                                   ##STR44##                 yellow                                         ______________________________________                                    

EXAMPLE 34

The procedure of Example 1 is repeated but 18.8 parts of β-hydroxynaphthoic acid is used as the coupling component. After coupling is over the whole is acidified and the product is suction filtered, washed with water and dried. 39.1 parts of the acid: ##STR45## is obtained. 24.6 parts of this acid is heated with 120 parts of trichlorobenzene, 2 parts of dimethylformamide and 25 parts of thionyl chloride for five hours at 100° to 110° C. The whole is cooled to ambient temperature and suction filtered, and the product is washed first with trichlorobenzene and then with cyclohexane and then dried. 22.4 parts of the acid chloride is obtained.

13.7 parts of this acid chloride in 120 parts of nitrobenzene has 6.5 parts of p-aminobenzanilide added to it and the whole is stirred for one hour at 90° C and for four hours at 130° C. The product is suction filtered at 80° C, washed with nitrobenzene and methanol and dried. 17.3 parts of a red powder of the formula ##STR46## is obtained.

Dyes having the hues specified in the following Table are obtained analogously to Example 34 with the amines set out in the Table.

    __________________________________________________________________________     Ex.                                                                            No. Amine                          Hue                                         __________________________________________________________________________     35                                                                                  ##STR47##                     red                                         36                                                                                  ##STR48##                     red                                         37                                                                                  ##STR49##                     red                                         38                                                                                  ##STR50##                     red                                         39                                                                                  ##STR51##                     red                                         40                                                                                  ##STR52##                     red                                         41                                                                                  ##STR53##                     bluish red                                  42                                                                                  ##STR54##                     yellowish red                               43                                                                                  ##STR55##                     yellowish red                               44                                                                                  ##STR56##                     bluish red                                  45                                                                                  ##STR57##                     red                                         46                                                                                  ##STR58##                     chestnut                                    47                                                                                  ##STR59##                     red                                         48                                                                                  ##STR60##                     red                                         49                                                                                  ##STR61##                     red                                         50                                                                                  ##STR62##                     red                                         51                                                                                  ##STR63##                     red                                         52                                                                                  ##STR64##                     chestnut                                    53                                                                                  ##STR65##                     Bordeaux                                    54                                                                                  ##STR66##                     bluish red                                  55                                                                                  ##STR67##                     bluish red                                  56                                                                                  ##STR68##                     red                                         57                                                                                  ##STR69##                     bluish red                                  58                                                                                  ##STR70##                     bluish red                                  59                                                                                  ##STR71##                     bluish red                                  60                                                                                  ##STR72##                     bluish red                                  61                                                                                  ##STR73##                     bluish red                                  62                                                                                  ##STR74##                     red                                         63                                                                                  ##STR75##                     yellowish red                               64                                                                                  ##STR76##                     red                                         65                                                                                  ##STR77##                     chestnut                                    66                                                                                  ##STR78##                     red                                         67                                                                                  ##STR79##                     red                                         68                                                                                  ##STR80##                     red                                         69                                                                                  ##STR81##                     bluish red                                  70                                                                                  ##STR82##                     bluish red                                  71                                                                                  ##STR83##                     bluish red                                  72                                                                                  ##STR84##                     red                                         73                                                                                  ##STR85##                     red                                         74                                                                                  ##STR86##                     chestnut                                    75                                                                                  ##STR87##                     yellowish red                               76                                                                                  ##STR88##                     violet                                      77                                                                                  ##STR89##                     yellowish red                               78                                                                                  ##STR90##                     red                                         79                                                                                  ##STR91##                     red                                         80                                                                                  ##STR92##                     yellowish red                               81                                                                                  ##STR93##                     chestnut                                    82                                                                                  ##STR94##                     bluish red                                  83                                                                                  ##STR95##                     bluish red                                  84                                                                                  ##STR96##                     bluish red                                  85                                                                                  ##STR97##                     bluish red                                  86                                                                                  ##STR98##                     bluish red                                  87                                                                                  ##STR99##                     bluish red                                  88                                                                                  ##STR100##                    bluish red                                  89                                                                                  ##STR101##                    bluish red                                  90                                                                                  ##STR102##                    bluish red                                  91                                                                                  ##STR103##                    bluish red                                  92                                                                                  ##STR104##                    bluish red                                  93                                                                                  ##STR105##                    bluish red                                  94                                                                                  ##STR106##                    bluish red                                  95                                                                                  ##STR107##                    bluish red                                  96                                                                                  ##STR108##                    bluish red                                  97                                                                                  ##STR109##                    bluish red                                  98                                                                                  ##STR110##                    bluish red                                  99                                                                                  ##STR111##                    bluish red                                  100                                                                                 ##STR112##                    bluish red                                  101                                                                                 ##STR113##                    bluish red                                  102                                                                                 ##STR114##                    bluish red                                  103                                                                                 ##STR115##                    bluish red                                  104                                                                                 ##STR116##                    bluish red                                  105                                                                                 ##STR117##                    bluish red                                  106                                                                                 ##STR118##                    bluish red                                  107                                                                                 ##STR119##                    bluish red                                  108                                                                                 ##STR120##                    bluish red                                  109                                                                                 ##STR121##                    bluish red                                  110                                                                                 ##STR122##                    red                                         111                                                                                 ##STR123##                    bluish red                                  112                                                                                 ##STR124##                    bluish red                                  114                                                                                 ##STR125##                    bluish red                                  __________________________________________________________________________ 

We claim:
 1. A compound of the formula ##STR126## in which: x is hydrogen, chloro, bromo, methyl or nitro;Y is hydrogen, chloro, bromo or methyl; K is CH₃ COCHCONHZ or ##STR127## Z is phenyl substituted by chloro, bromo, methyl, ethyl, methoxy, ethoxy, acetylamino, propionylamino, benzoylamino, chlorobenzoylamino or dichlorobenzoylamino; or ##STR128## A is ##STR129## C₁ to C₄ alkyl; phenyl; phenyl which is ring-substituted by chloro, bromo, methyl, ethyl, methoxy, ethoxy, cyano, carbamoyl, N-phenylcarbamoyl, N-chlorophenylcarbamoyl, N-bromophenylcarbamoyl, N-methylphenylcarbamoyl, N-methoxyphenylcarbamoyl, N-ethoxyphenylcarbamoyl, C₁ to C₄ alkoxycarbonyl or sulfamoyl; naphthyl; anthraquinonyl; amino; C₁ to C₅ alkylamino; benzylamino; phenylamino; phenylamino which is ring-substituted by chloro, bromo, methyl, ethyl, methoxy, ethoxy or carbamoyl; naphthylamino; anthraquinonylamino; phenoxy; or phenoxy substituted by chloro, bromo, methyl, ethyl, methoxy or ethoxy; R¹ is hydrogen, chloro, bromo, C₁ to C₄ alkyl, C₁ to C₄ alkoxy, phenyl, methylsulfonyl, ethylsulfonyl, carbamoyl or sulfamoyl; R² is hydrogen, chloro, bromo, methyl, ethyl, methoxy or ethoxy; R³ is hydrogen, chloro, bromo, methyl or ethyl; and R⁴ is hydrogen, chloro, bromo, methyl, ethyl, methoxy or ethoxy.
 2. A dye as claimed in claim 1 of the formula: ##STR130## in which R¹ is hydrogen, chloro, bromo, C₁ to C₄ alkyl, C₁ to C₄ alkoxy, phenyl, methylsulfonyl, ethylsulfonyl, carbamoyl or sulfamoyl;R² is hydrogen, chloro, bromo, methyl, ethyl, methoxy or ethoxy; R³ is hydrogen, chloro, bromo, methyl or ethyl; and R⁴ is hydrogen, chloro, bromo, methyl, ethyl, methoxy or ethoxy.
 3. A compound as claimed in claim 1 of the formula: ##STR131## in which: A¹ is C₁ to C₄ alkyl; phenyl substituted by chloro, bromo, methyl, ethyl, methoxy, ethoxy, cyano, carbamoyl, N-phenylcarbamoyl, N-chlorophenylcarbamoyl, N-bromophenylcarbamoyl, N-methylphenylcarbamoyl, N-methoxyphenylcarbamoyl, N-ethoxyphenylcarbamoyl, C₁ to C₄ alkoxycarbonyl or sulfamoyl; naphthyl; anthraquinonyl; amino; C₁ to C₅ alkylamino; benzylamino; phenylamino; phenylamino substituted by chloro, bromo, methyl, ethyl, methoxy, ethoxy or carbamoyl; naphthylamino; anthraquinonylamino; phenoxy; or phenoxy substituted by chloro, bromo, methyl, ethyl, methoxy or ethoxy.
 4. The compound as claimed in claim 1 of the formula: ##STR132## 